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Stimuli-responsive inorganic–organic hybrid metal halides (IOMHs) have shown great potential in sensing, information encryption and anti-counterfeiting, etc. However, the stimuli-responsive behavior based on the regulation of the functional groups in organic species is still blank in IOMHs. Herein, three zero-dimensional (0-D) antimony-based IOMHs with different functional groups in the organic cations are reported, namely [AOEMIm]3SbCl6 (1, AOEMIm = 1-acetoxyethyl-3 methylimidazolium), [HOOCMMIm]3SbCl6·3(OOCMMIm) (2, HOOCMMIm = 1-carboxymethyl-3-methylimidazolium) and [HOOCMMIm]3SbCl6 (3). Photophysical characterizations show that 1, 2 and 3 exhibit typical self-trapped exciton triplet broadband emission, peaking at 610, 510 and 525 nm under excitation of 365 nm, 375 nm and 345 nm, respectively. Under the H2O stimulation, the organic groups in the crystal structures undergo a mutual transformation, that is, from acetoxyethyl or carboxyl to a mixture of carboxyl and deprotonated carboxyl. Accordingly, the organic group switching is accompanied by a solid–solid transformation from 1 or 2 to 3 crystals. The intrinsic mechanism for the phase transition is expounded as well. Due to the obvious luminescence change from yellow-green emission (3) to green emission (2), 3 is further applied in the detection of trace water in organic solvents. The water detection limit in tetrahydrofuran (THF) is as low as 0.3% v/v. This study provides a new avenue for the construction of stimuli-responsive IOMHs. [ABSTRACT FROM AUTHOR]

Herein, the first F-containing iodate-phosphate, namely Ba2Ga2F6(IO3)(PO4), was prepared via a hydrothermal reaction, in which HPF6 (70 wt% solution in water) was used as the source of both fluoride and phosphate anions for the first time. Ba2Ga2F6(IO3)(PO4) features an unprecedented 1D [Ga2F6(IO3)(PO4)]4− helix chain, composed of a 1D Ga(1)(IO3)O4F chain via the bridging of 0D Ga(2)(PO4)F5. The UV-Vis spectrum shows that Ba2Ga2F6(IO3)(PO4) has a wide bandgap with a short-UV absorption edge (4.35 eV; 253 nm). Birefringence measurement under a polarizing microscope shows that Ba2Ga2F6(IO3)(PO4) displays a moderate birefringence of 0.072@550 nm, which is consistent with the value (0.070@550 nm) obtained by DFT calculations, indicating that Ba2Ga2F6(IO3)(PO4) has potential applications as a short-UV birefringent material. This study highlights the crucial role played by the incorporation of specific functional groups into compounds, shedding light on their contribution to promising inorganic functional materials. [ABSTRACT FROM AUTHOR]

Single-component white-light materials have received much attention due to the rise of white light emitting diodes (WLEDs). Inorganic–organic hybrid metal halides (IOMHs) are considered excellent candidates for single-component white-light materials due to their rich structural tunability and excellent photoluminescence properties. Here, we put forward a strategy to realize effective single-component white-light emission, that is, incorporating a bipyididyl-type emissive ligand into the anionic halometallic unit of an ionic zero-dimensional (0-D) IOMH. As demonstated by the construction of a 0-D In(III)-based IOMH, namely [Ammim][InCl4(dmbp)] (Ammim = 1-allyl-2,3-dimethylimidazolium, dmbp = 4,4′-dimethyl-2,2′-bipyridyl), after partially replacing the chlorine atoms in the chloroindate unit with a dmbp ligand, the resultant compound exhibits broadband white light emission under UV excitation with a photoluminescence quantum yield (PLQY) of 16.70% and a color rendering index (CRI) of 93.2. Systematic studies demonstrate that the source of white light is the charge transfer from the inorganic part to the bipyididyl-type ligand. Our work provides a new path for designing single-component white-light materials with superior photophysical properties. [ABSTRACT FROM AUTHOR]

Lead-based two-dimensional organic–inorganic hybrid perovskites (2D HOIPs) are popular materials with various optical properties, which can be tuned through metal ion doping. Due to the size and valence misfit, metal ion dopants in 2D lead-based HOIPs are still limited. In this work, Mn2+, Sb3+ and Bi3+ are doped into 2D (HDA)2PbBr4 (HDA = protonated dopamine) successfully. As a result, the dopants in 2D (HDA)2PbBr4 can induce their characteristic optical spectra, which is studied at different temperatures and excitation powers. The temperature-dependent energy transfer in the Mn-doped sample has been clarified, in which abnormal phenomena including negative thermal quenching have been observed. In addition, the dopant ions can impact the phase transition temperatures of the samples, especially lowering their crystallization temperatures greatly. The mussel-inspired organic cation, feasible metal ion regulation, and superior stability provide (HDA)2PbBr4 potential for further applications. [ABSTRACT FROM AUTHOR]

In this paper, we synthesized layered crystals of bis(μ2-chlor)-tris(triphenylphosphine)-di-copper(I) (CTC) and bis(μ2-bromo)-tris(triphenylphosphine)-di-copper(I) (BTC) via electrochemical synthesis in an ambient environment. The crystal stands edge-on to the copper substrate in the electrochemical synthesis, which would enhance the charge transfer between the crystal and the substrate, promoting its photoelectric properties. Combined with density functional theory calculations, the optical absorption and emission are the crystals were studied to obtain a clarified mechanism. Using a chemical etching strategy, we can obtain BTC microtubes with tunable cavities, which can be used as microscopic containers. [ABSTRACT FROM AUTHOR]

Layered heterostructures have gained significant attention as potential platforms for energy storage because of their unique electronic and interfacial characteristics. Engineering heterojunctions in a rational, efficient, and effective manner is critical to well-defined battery systems. Herein, FePSe3–FeSe2 heterojunctions uniformly dispersed in a Ketjen black carbon matrix (FePSe3–FeSe2/C) were prepared by a one-step phosphorization–selenization method. The conductive carbon matrix can prevent the aggregation of FePSe3–FeSe2 hexagonal nanoplatelets. Moreover, theoretical calculations demonstrate that FePSe3–FeSe2 heterostructures with a strong asymmetric electric field can facilitate K+ intercalation. Notably, FePSe3–FeSe2/C with rich active sites would undergo negative fading, which results in a capacity increase upon cycling. As an anode for potassium ion batteries (PIBs), FePSe3–FeSe2/C can deliver high capacities of 352 mA h g−1 at 0.1 A g−1 after 100 cycles and 224 mA h g−1 at 1.0 A g−1 after 3700 cycles. The strategy of fabricating FePSe3–FeSe2 heterojunctions can be extended to other metal phosphorus trichalcogenides to improve their performance in energy storage. Furthermore, the obtained results provide important insights into hetero-nanostructure design toward fast reaction kinetics for PIBs. [ABSTRACT FROM AUTHOR]

Zero-dimensional (0D) organic–inorganic metal halides (OIMHs) hold promise in photoluminescence properties and related applications. Thus far, the photoluminescence quantum yields (PLQYs) of the reported 0D hybrid antimony(III) bromides (HABs) are not as high as those of the chloride analogs; therefore, the improvement of PLQY is an important issue for luminescent HABs. Herein, a supramolecular interaction adjustment strategy to improve the PLQYs of HABs is proposed. Two isostructural 0D HABs that crystallize with different lattice solvent molecules, namely [EtPPh3]2[SbBr5]·EtOH (1·EtOH-Br; EtPPh3 = ethyltriphenylphosphonium; EtOH = ethanol) and [EtPPh3]2[SbBr5]·MeCN (1·MeCN-Br; MeCN = acetonitrile), have been synthesized. Both of them exhibit typical self-trapped exciton (STE) photoluminescence (PL) with broad emission, a large Stokes shift and a long lifetime. They show deviation in deep-red emission peaks (655 nm vs. 661 nm) owing to the difference in the distortion level of [SbBr5]2− anions. Most importantly, 1·EtOH-Br exhibits a nearly one-fold enhancement in PLQY compared to 1·MeCN-Br (18.26% vs. 9.29%). Density functional theory (DFT) calculations, hydrogen bonding analysis and Hirshfeld surface analysis suggest that the PLQY enhancement is due to the structural rigidity improvement brought by hydrogen bonding adjustments between the inorganic [SbBr5]2− anions and solvent molecules. This work provides a new insight into the structure–property relationship study and PLQY improvement for 0D OIMHs. [ABSTRACT FROM AUTHOR]

Although luminescent indium(III) based halide perovskites have been widely investigated, the study of emissive indium(III) halide hybrids is limited. Three indium(III) chloride hybrids based on a bpym ligand were synthesized, namely [EPy]2[InCl4(bpym)InCl4]·DMF (1), [EPy]2[InCl4(bpym)InCl4] (2), and [BPy]2[InCl4(bpym)InCl4] (3) (EPy = N-ethylpyridinium; BPy = N-butylpyridinium; bpym = 2,2′-bipyrimidine). They all exhibit a zero-dimensional structure, in which the ligand bpym interconnects two [InCl4]− to form a [InCl4(bpym)InCl4]2− anion that is further charge-compensated by the corresponding pyridinium cations. This is the first time using bpym to coordinate with an In atom. At 298 K, 1 exhibits a weak emission at 600 nm while 2 and 3 exhibit emissions peaking at 500 nm and 540 nm, respectively. Interestingly, the DMF solvent molecule in 1 can be removed by heating, thus resulting in the structural transformation of 1 into 2 together with a photoluminescence (PL) change. Density functional theory (DFT) calculations confirm that halogen-to-ligand charge-transfer (HLCT) occurs in the emission process. To the best of our knowledge, this is the first report on PL of ionic indium(III) halide hybrids incorporating organic ligands. [ABSTRACT FROM AUTHOR]

Three bismuth(III) bromide hybrids based on 2,2′-bipyridyl-1,1′-dioxide (bp2do) were obtained by a solvothermal method, namely Bi2Br6(bp2do)2 (1), Bi2Br6(bp2do)2·0.5CH3CN (2), and [PP14][BiBr4(bp2do)] (3, PP14 = 1-butyl-1-methylpiperidinium). 1 features a centrosymmetric [Bi2Br6O4] dimer, in which two identical [BiBr4O2] octahedra edge-share two Br atoms; 2 contains a [Bi2Br6O4] dinuclear unit with a unique configuration, in which a [BiBr4O2] octahedron face-shares one Br and two O atoms with a [BiBr3O4] pentagonal-bipyramid. Moreover, the metal–ligand linking mode adopted in 2 has not been reported before. The choice of organic solvents could induce different Bi–Br–bp2do geometries with a dimer in 1 and a dinuclear unit in 2. Introduction of ionic liquid cations resulted in the ionic compound 3 featuring a mononuclear [BiBr4(bp2do)] unit. A more rigid environment with more hydrogen bonds leads to visible green phosphorescence with long lifetime for 3 under UV light. The three compounds possess similar phosphorescence peaks at 77 K, which originates from inorganic-to-organic charge transfer (IOCT) as confirmed by density functional theory (DFT) calculations. [ABSTRACT FROM AUTHOR]

Zero-dimensional (0D) organic–inorganic hybrid metal halides (OIMHs) containing multiple halometallate species (HMSs) have received extensive attention due to their capability to achieve multifunctional photophysical characteristics. Herein we report a lead-free 0D-OIMH compound, namely [Emim]8[SbCl6]2[SbCl5] (1, Emim = 1-ethyl-3-methylimidazolium), which is the first crystal containing two distinct mononuclear [SbXn]3−n units in one single structure. The optical absorption, temperature/excitation-variable photoluminescence (PL) and PL decay were studied. 1 exhibits a broad emission centered at 577 nm, which is analyzed to be a combination of the emissions from [SbCl6]3− and [SbCl5]2−. The structural effects including Sb⋯Sb distances and polyhedral distortion of [SbXn]3−n on the PL of antimony-based 0D-OIMHs are discussed in detail. This work would provide guidance for constructing Sb-based 0D OIMHs composed of multiple halometallate species. [ABSTRACT FROM AUTHOR]

CsMnCl3(H2O)2 (CMCH) has been widely investigated for magnetic and optical applications, including anti-Stokes photoluminescence, microwave absorption, and magnon-assisted optical transitions. Herein, CMCH crystals, which are colorless and transparent (unlike the pink crystals reported previously), were obtained through a unique approach. Consequently, a high-resolution optical absorption spectrum and distinct thermal behavior were observed. The reversible (de)hydration of CMCH being accompanied by photoluminescence switching (mainly in terms of the color temperature) was rationalized using crystal structure analysis. As a result, water-soluble CMCH could be applied as a moisture-responsive luminescent ink. Moreover, density functional theory (DFT) calculations were performed to understand the optical absorption of CMCH. [ABSTRACT FROM AUTHOR]

Two chlorobismuthate hybrids incorportating ionic liquid cations (ILCs) with second-level room-temperature phosphorescence (RTP), namely [Emim]BiCl4(bp2do) (1) and [Emmim]BiCl4(bp2do) (2) (Emim = 1-ethyl-3-methylimidazolium, Emmim = 1-ethyl-2,3-dimethylimidazolium, bp2do = 2,2′-bipyridyl-1,1′-dioxide), were obtained. The decrease in the number of substituents in the ILCs largely enhanced the phosphorescence quantum yield (QY) from 2.31% for 2 to 25.05% for 1, owing to the more compact structure of 1. The two compounds possess uncommonly different temperature-dependent emission peak shifting behaviors, which could be ascribed to whether the electron-phonon interactions or the exciton localization at high energy is dominant. Density functional theory (DFT) calculations show that the optical absorptions for both compounds originate from inorganic moiety to organic moiety charge transfer (IOCT). X-ray scintillation was observed for both compounds, which is the first report on inorganic–organic halobismuthate hybrids. Finally, 1 with higher QY was fabricated into a luminescent thin flim, letters and a bendable round wafer with polyacrylonitrile (PAN). This work provides new insight on RTP materials and X-ray scintillation materials involving bismuth halides. [ABSTRACT FROM AUTHOR]

Herein, a zero-dimensional (0D) hybrid organic–inorganic metal halide (OIMH) [BPy]6[Pb3Br12] (BPB, BPy = N-butylpyridinium) as a room-temperature phosphorescent (RTP) material is synthesized. Through molecular sensitization, its RTP quantum efficiency can be increased by a maximum of 14-fold. A white-light-emitting device is obtained via a solvent-free and eco-friendly melting method. [ABSTRACT FROM AUTHOR]

The different hydrogen bond interactions in two organic–inorganic hybrid manganese halide compounds, namely [A]2[MnBr4] (A = N-butyl-N-methylpyrrolidinium ([P14]+) for (1) and N-butyl-N-methylpiperidinium ([PP14]+) for (2)), lead to distinct photoluminescence quantum yields (81% for 1; 55% for 2). Further applications of luminescent 1 are also developed. [ABSTRACT FROM AUTHOR]

Differences in the electronegativity and hydrophilicity of halogens lead to differences in proton-conducting and photoluminescence properties in hybrid organic–inorganic lead halide compounds of [PbX2(OOCMMIm)]n (X = Cl (1), Br (2), HOOCMMIm = 1-carboxymethyl-3-methylimidazolium). [ABSTRACT FROM AUTHOR]

CdS synthesis by plasma-enhanced microwave physical vapor transport (PMPVT) has been developed in this work. The photoluminescence (PL), absorbance, Raman spectra and the mechanism of CdS crystal growth have been investigated. Furthermore, plasma-enhanced microwave chemical vapour transport (PMCVT) synthesis of CdS with additional chemical transport agents has been explored. In addition, other II–VI chalcogenides were also synthesized by PMPVT. [ABSTRACT FROM AUTHOR]

The removal of highly radioactive and long-lived 137Cs+ and 90Sr2+ from solution is of significance for radionuclide remediation. Herein we prepared a two-dimensionally microporous thiostannate, namely (Me2NH2)4/3(Me3NH)2/3Sn3S7·1.25H2O (FJSM-SnS), and systematically investigated its Cs+ and Sr2+ ion-exchange performance in different conditions. The structural stabilities and variation, ion-exchange kinetic and isothermal behavior, pH-dependent distribution coefficients (Kd), ion-exchange in simulated groundwater and ion-exchange applied to chromatography have been investigated. The results indicated that the maximum Cs+ and Sr2+ ion-exchange capacities of FJSM-SnS were 408.91 mg g−1 and 65.19 mg g−1, respectively. In particular, FJSM-SnS showed quick ion-exchange ability and wide pH resistance (0.7–12.7) which make it outstanding among the ion-exchangers. An ion-exchange chromatographic column was firstly studied for chalcogenido ion-exchange materials, that is, a column filled with 3.0 g FJSM-SnS could remove 96–99% of Cs+ ion and near 100% of Sr2+ ion at low ionic concentrations in 900 bed volumes solutions. Furthermore, the title material could be synthesized on a large scale by a facile, one-pot and economical solvothermal method. The relatively low cost but remarkable ion-exchange performance makes it promising for radionuclide remediation. [ABSTRACT FROM AUTHOR]

Lead-based two-dimensional organic–inorganic hybrid perovskites (2D HOIPs) are popular materials with various optical properties, which can be tuned through metal ion doping. Due to the size and valence misfit, metal ion dopants in 2D lead-based HOIPs are still limited. In this work, Mn2+, Sb3+ and Bi3+ are doped into 2D (HDA)2PbBr4 (HDA = protonated dopamine) successfully. As a result, the dopants in 2D (HDA)2PbBr4 can induce their characteristic optical spectra, which is studied at different temperatures and excitation powers. The temperature-dependent energy transfer in the Mn-doped sample has been clarified, in which abnormal phenomena including negative thermal quenching have been observed. In addition, the dopant ions can impact the phase transition temperatures of the samples, especially lowering their crystallization temperatures greatly. The mussel-inspired organic cation, feasible metal ion regulation, and superior stability provide (HDA)2PbBr4 potential for further applications. [ABSTRACT FROM AUTHOR]

Herein, the first F-containing iodate-phosphate, namely Ba 2 Ga 2 F 6 (IO 3 )(PO 4 ), was prepared via a hydrothermal reaction, in which HPF 6 (70 wt% solution in water) was used as the source of both fluoride and phosphate anions for the first time. Ba 2 Ga 2 F 6 (IO 3 )(PO 4 ) features an unprecedented 1D [Ga 2 F 6 (IO 3 )(PO 4 )] 4- helix chain, composed of a 1D Ga(1)(IO 3 )O 4 F chain via the bridging of 0D Ga(2)(PO 4 )F 5 . The UV-Vis spectrum shows that Ba 2 Ga 2 F 6 (IO 3 )(PO 4 ) has a wide bandgap with a short-UV absorption edge (4.35 eV; 253 nm). Birefringence measurement under a polarizing microscope shows that Ba 2 Ga 2 F 6 (IO 3 )(PO 4 ) displays a moderate birefringence of 0.072@550 nm, which is consistent with the value (0.070@550 nm) obtained by DFT calculations, indicating that Ba 2 Ga 2 F 6 (IO 3 )(PO 4 ) has potential applications as a short-UV birefringent material. This study highlights the crucial role played by the incorporation of specific functional groups into compounds, shedding light on their contribution to promising inorganic functional materials.

Lead-based two-dimensional organic-inorganic hybrid perovskites (2D HOIPs) are popular materials with various optical properties, which can be tuned through metal ion doping. Due to the size and valence misfit, metal ion dopants in 2D lead-based HOIPs are still limited. In this work, Mn 2+ , Sb 3+ and Bi 3+ are doped into 2D (HDA) 2 PbBr 4 (HDA = protonated dopamine) successfully. As a result, the dopants in 2D (HDA) 2 PbBr 4 can induce their characteristic optical spectra, which is studied at different temperatures and excitation powers. The temperature-dependent energy transfer in the Mn-doped sample has been clarified, in which abnormal phenomena including negative thermal quenching have been observed. In addition, the dopant ions can impact the phase transition temperatures of the samples, especially lowering their crystallization temperatures greatly. The mussel-inspired organic cation, feasible metal ion regulation, and superior stability provide (HDA) 2 PbBr 4 potential for further applications.

In this study, we identify a novel class of second-order nonlinear optical (NLO) crystals, non-π-conjugated piperazine (H 10 C 4 N 2 , PIP) metal halides, represented by two centimeter-sized, noncentrosymmetric organic-inorganic metal halides (OIMHs), namely H 12 C 4 N 2 CdI 4 ( P 2 1 2 1 2 1 ) and H 11 C 4 N 2 CdI 3 ( Cc ). H 12 C 4 N 2 CdI 4 is the first to be prepared, and its structure contains a CdI 4 tetrahedron, which led to a poor NLO performance, including a weak and non-phase-matchable second harmonic generation (SHG) response of 0.5 × KH 2 PO 4 (KDP), a small birefringence of 0.047 @1064 nm and a narrow bandgap of 3.86 eV. Moreover, H 12 C 4 N 2 CdI 4 is regarded as the model compound, and we further obtain H 11 C 4 N 2 CdI 3 via the replacement of CdI 4 with a highly polarizable CdNI 3 tetrahedron, which results in a sharp enhancement of SHG response and birefringence. H 11 C 4 N 2 CdI 3 exhibits a promising NLO performance including 6 × KDP, 4.10 eV, Δ n = 0.074 @1064 nm and phase matchability, indicating that it is the first OIMH to simultaneously exhibit strong SHG response (>5 × KDP) and a wide bandgap (>4.0 eV). Our work presents a novel direction for designing high-performance NLO crystals based on organic-inorganic halides and provides important insights into the role of the hybridized tetrahedron in enhancing the SHG response and birefringence., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Zero-dimensional (0D) organic-inorganic metal halides (OIMHs) hold promise in photoluminescence properties and related applications. Thus far, the photoluminescence quantum yields (PLQYs) of the reported 0D hybrid antimony(III) bromides (HABs) are not as high as those of the chloride analogs; therefore, the improvement of PLQY is an important issue for luminescent HABs. Herein, a supramolecular interaction adjustment strategy to improve the PLQYs of HABs is proposed. Two isostructural 0D HABs that crystallize with different lattice solvent molecules, namely [EtPPh 3 ] 2 [SbBr 5 ]·EtOH (1·EtOH-Br; EtPPh 3 = ethyltriphenylphosphonium; EtOH = ethanol) and [EtPPh 3 ] 2 [SbBr 5 ]·MeCN (1·MeCN-Br; MeCN = acetonitrile), have been synthesized. Both of them exhibit typical self-trapped exciton (STE) photoluminescence (PL) with broad emission, a large Stokes shift and a long lifetime. They show deviation in deep-red emission peaks (655 nm vs. 661 nm) owing to the difference in the distortion level of [SbBr 5 ] 2- anions. Most importantly, 1·EtOH-Br exhibits a nearly one-fold enhancement in PLQY compared to 1·MeCN-Br (18.26% vs. 9.29%). Density functional theory (DFT) calculations, hydrogen bonding analysis and Hirshfeld surface analysis suggest that the PLQY enhancement is due to the structural rigidity improvement brought by hydrogen bonding adjustments between the inorganic [SbBr 5 ] 2- anions and solvent molecules. This work provides a new insight into the structure-property relationship study and PLQY improvement for 0D OIMHs.

Compound [C 5 mim][Mim] 2 [SbCl 6 ] (1; [C 5 mim] + = 1-pentyl-3-methylimidazolium; [Mim] + = N -methylimidazolium) with dual cations exhibits the first case of deep-red emission in [SbCl 6 ] 3- -based 0D OIMHs. Anion distortion due to high disequilibrium of supramolecular interactions is revealed to be responsible for the extremely large Stokes shift of 335 nm and FWHM of 210 nm in the emission.

Although luminescent indium(III) based halide perovskites have been widely investigated, the study of emissive indium(III) halide hybrids is limited. Three indium(III) chloride hybrids based on a bpym ligand were synthesized, namely [EPy] 2 [InCl 4 (bpym)InCl 4 ]·DMF (1), [EPy] 2 [InCl 4 (bpym)InCl 4 ] (2), and [BPy] 2 [InCl 4 (bpym)InCl 4 ] (3) (EPy = N -ethylpyridinium; BPy = N -butylpyridinium; bpym = 2,2'-bipyrimidine). They all exhibit a zero-dimensional structure, in which the ligand bpym interconnects two [InCl 4 ] - to form a [InCl 4 (bpym)InCl 4 ] 2- anion that is further charge-compensated by the corresponding pyridinium cations. This is the first time using bpym to coordinate with an In atom. At 298 K, 1 exhibits a weak emission at 600 nm while 2 and 3 exhibit emissions peaking at 500 nm and 540 nm, respectively. Interestingly, the DMF solvent molecule in 1 can be removed by heating, thus resulting in the structural transformation of 1 into 2 together with a photoluminescence (PL) change. Density functional theory (DFT) calculations confirm that halogen-to-ligand charge-transfer (HLCT) occurs in the emission process. To the best of our knowledge, this is the first report on PL of ionic indium(III) halide hybrids incorporating organic ligands.

Zero-dimensional (0D) organic-inorganic hybrid metal halides (OIMHs) containing multiple halometallate species (HMSs) have received extensive attention due to their capability to achieve multifunctional photophysical characteristics. Herein we report a lead-free 0D-OIMH compound, namely [Emim]8[SbCl6]2[SbCl5] (1, Emim = 1-ethyl-3-methylimidazolium), which is the first crystal containing two distinct mononuclear [SbXn]3-n units in one single structure. The optical absorption, temperature/excitation-variable photoluminescence (PL) and PL decay were studied. 1 exhibits a broad emission centered at 577 nm, which is analyzed to be a combination of the emissions from [SbCl6]3- and [SbCl5]2-. The structural effects including SbSb distances and polyhedral distortion of [SbXn]3-n on the PL of antimony-based 0D-OIMHs are discussed in detail. This work would provide guidance for constructing Sb-based 0D OIMHs composed of multiple halometallate species.

CsMnCl3(H2O)2 (CMCH) has been widely investigated for magnetic and optical applications, including anti-Stokes photoluminescence, microwave absorption, and magnon-assisted optical transitions. Herein, CMCH crystals, which are colorless and transparent (unlike the pink crystals reported previously), were obtained through a unique approach. Consequently, a high-resolution optical absorption spectrum and distinct thermal behavior were observed. The reversible (de)hydration of CMCH being accompanied by photoluminescence switching (mainly in terms of the color temperature) was rationalized using crystal structure analysis. As a result, water-soluble CMCH could be applied as a moisture-responsive luminescent ink. Moreover, density functional theory (DFT) calculations were performed to understand the optical absorption of CMCH.

The different hydrogen bond interactions in two organic-inorganic hybrid manganese halide compounds, namely [A]2[MnBr4] (A = N-butyl-N-methylpyrrolidinium ([P14]+) for (1) and N-butyl-N-methylpiperidinium ([PP14]+) for (2)), lead to distinct photoluminescence quantum yields (81% for 1; 55% for 2). Further applications of luminescent 1 are also developed.

Differences in the electronegativity and hydrophilicity of halogens lead to differences in proton-conducting and photoluminescence properties in hybrid organic-inorganic lead halide compounds of [PbX 2 (OOCMMIm)] n (X = Cl (1), Br (2), HOOCMMIm = 1-carboxymethyl-3-methylimidazolium).

Presented here are three organic-decorated manganese selenidostannates with various structural dimensionalities (D), namely, 1D – SnSe3Mn(en)2 (en = ethylenediamine) (1), 2D – SnSe3Mn(en) (2) and 3D – MnSnSe4Mn(en)2 (3). 2 and 3 represent the first 2D and 3D organic-decorated Mn–Sn–Se compounds, respectively. A structural transformation was observed between 1 and 2.

Two mixed-valent thioarsenates, namely (enH2)(4.5)[In(As(V)S4)3][As2(III)(μ-S2)S3]Cl (1) and (enH2)MnAs(III)As(V)S6 (2) (en = ethylenediamine), have been solvothermally synthesized and characterized. Thermal stability, magnetic and mixed-valent optical properties, as well as theoretical band structures and DOSs, of 1 and 2 have also been studied.